This research program focuses on the development of new synthetic methodology involving pericyclic reactions. Accelerated sigmatropic rearrangements of vinylcyclopropane and vinylcyclobutane derivatives are being investigated. These reactions are applied in new stereoselective annulation approaches to cyclopentene and cyclohexene derivatives. Electrocyclic reactions and (2 plus 2) and (4 plus 2) cycloadditions of vinylketenes are being examined as new methods for the synthesis of alicyclic and aromatic compounds. The synthetic utility of these pericyclic reactions is being demonstrated in efficient total syntheses of sesquiterpenes, antifungal phenols, and naturally occurring anthracyclines.